JPH04170351A - Resin composition for scagliola - Google Patents
Resin composition for scagliolaInfo
- Publication number
- JPH04170351A JPH04170351A JP29491690A JP29491690A JPH04170351A JP H04170351 A JPH04170351 A JP H04170351A JP 29491690 A JP29491690 A JP 29491690A JP 29491690 A JP29491690 A JP 29491690A JP H04170351 A JPH04170351 A JP H04170351A
- Authority
- JP
- Japan
- Prior art keywords
- glass powder
- average particle
- particle size
- weight
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011342 resin composition Substances 0.000 title claims description 15
- 239000000843 powder Substances 0.000 claims abstract description 43
- 239000011521 glass Substances 0.000 claims abstract description 42
- 239000002245 particle Substances 0.000 claims abstract description 30
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000002928 artificial marble Substances 0.000 claims description 20
- 229920006337 unsaturated polyester resin Polymers 0.000 claims description 15
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 6
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- 239000000178 monomer Substances 0.000 abstract description 5
- 239000002562 thickening agent Substances 0.000 abstract description 4
- 239000003086 colorant Substances 0.000 abstract description 3
- 229920000728 polyester Polymers 0.000 abstract description 3
- 229920005989 resin Polymers 0.000 abstract description 2
- 239000011347 resin Substances 0.000 abstract description 2
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 abstract description 2
- 229920001225 polyester resin Polymers 0.000 abstract 2
- 239000004645 polyester resin Substances 0.000 abstract 2
- 239000003638 chemical reducing agent Substances 0.000 abstract 1
- 239000012744 reinforcing agent Substances 0.000 abstract 1
- 239000000945 filler Substances 0.000 description 8
- 238000000465 moulding Methods 0.000 description 8
- 239000002253 acid Substances 0.000 description 6
- -1 triethylene glycol, hydrogenated bisphenol A Chemical class 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000004412 Bulk moulding compound Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000003677 Sheet moulding compound Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000006082 mold release agent Substances 0.000 description 3
- 239000012779 reinforcing material Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 229920006305 unsaturated polyester Polymers 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- DJKGDNKYTKCJKD-BPOCMEKLSA-N (1s,4r,5s,6r)-1,2,3,4,7,7-hexachlorobicyclo[2.2.1]hept-2-ene-5,6-dicarboxylic acid Chemical compound ClC1=C(Cl)[C@]2(Cl)[C@H](C(=O)O)[C@H](C(O)=O)[C@@]1(Cl)C2(Cl)Cl DJKGDNKYTKCJKD-BPOCMEKLSA-N 0.000 description 1
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 1
- KDGNCLDCOVTOCS-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy propan-2-yl carbonate Chemical compound CC(C)OC(=O)OOC(C)(C)C KDGNCLDCOVTOCS-UHFFFAOYSA-N 0.000 description 1
- ZQHJVIHCDHJVII-OWOJBTEDSA-N (e)-2-chlorobut-2-enedioic acid Chemical compound OC(=O)\C=C(\Cl)C(O)=O ZQHJVIHCDHJVII-OWOJBTEDSA-N 0.000 description 1
- ROLAGNYPWIVYTG-UHFFFAOYSA-N 1,2-bis(4-methoxyphenyl)ethanamine;hydrochloride Chemical compound Cl.C1=CC(OC)=CC=C1CC(N)C1=CC=C(OC)C=C1 ROLAGNYPWIVYTG-UHFFFAOYSA-N 0.000 description 1
- PXLYROINIXKFAW-UHFFFAOYSA-N 1-(3-bromophenyl)-2-(methylamino)propan-1-one Chemical compound CNC(C)C(=O)C1=CC=CC(Br)=C1 PXLYROINIXKFAW-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- CISIJYCKDJSTMX-UHFFFAOYSA-N 2,2-dichloroethenylbenzene Chemical compound ClC(Cl)=CC1=CC=CC=C1 CISIJYCKDJSTMX-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- XIRDTMSOGDWMOX-UHFFFAOYSA-N 3,4,5,6-tetrabromophthalic acid Chemical compound OC(=O)C1=C(Br)C(Br)=C(Br)C(Br)=C1C(O)=O XIRDTMSOGDWMOX-UHFFFAOYSA-N 0.000 description 1
- WZHHYIOUKQNLQM-UHFFFAOYSA-N 3,4,5,6-tetrachlorophthalic acid Chemical compound OC(=O)C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C(O)=O WZHHYIOUKQNLQM-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- ZDNFTNPFYCKVTB-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,4-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=C(C(=O)OCC=C)C=C1 ZDNFTNPFYCKVTB-UHFFFAOYSA-N 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- SZKXDURZBIICCF-UHFFFAOYSA-N cobalt;pentane-2,4-dione Chemical compound [Co].CC(=O)CC(C)=O SZKXDURZBIICCF-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、人造大理石用樹脂組成物に関し、詳しくは、
透明性及び表面平滑性にすぐれると共に、表面硬度にも
すぐれる人造大理石用不飽和ポリエステル樹脂組成物に
関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a resin composition for artificial marble.
This invention relates to an unsaturated polyester resin composition for use in artificial marble, which has excellent transparency and surface smoothness, as well as excellent surface hardness.
（従来の技術）
従来、種々の充填材を不飽ポリエステル樹脂に配合し、
硬化させてなる成形品は、人造大理石として、浴槽、洗
面カウンター、キッチンカウンター、テーブル等に広く
用いられている。これらは、シートモールデイングコン
パウンド（以下、ＳＭＣと略する。）やバルクモールデ
ィングコンパウンド（以下、ＢＭＣと略する。）等を用
いるプレス成形によって製造されている。(Prior art) Conventionally, various fillers were blended with unsaturated polyester resin,
The hardened molded product is widely used as artificial marble for bathtubs, sink counters, kitchen counters, tables, etc. These are manufactured by press molding using a sheet molding compound (hereinafter abbreviated as SMC), a bulk molding compound (hereinafter abbreviated as BMC), or the like.
しかし、このように不飽和ポリエステル樹脂を基材樹脂
とする人造大理石は、アクリル樹脂、エポキシ樹脂、フ
ェノール樹脂等を基材樹脂とするものに比べて表面硬度
が低いために表面に疵が付きやすい。However, artificial marble made of unsaturated polyester resin as a base resin has a lower surface hardness than those made of acrylic resin, epoxy resin, phenol resin, etc., and is therefore prone to scratches on the surface. .
また、従来、充填材として、水酸化アルミニラ、ムは、
透明性、難燃性、価格、白色度等にバランスよくすぐれ
ており、広く用いられているが、得られる成形品は、表
面硬度が不十分であって、この点からも、成形品の表面
に疵が付きやすい。In addition, conventionally, aluminum hydroxide was used as a filler.
Although it is widely used because it has a good balance of transparency, flame retardancy, price, whiteness, etc., the resulting molded product has insufficient surface hardness. easily scratched.
そこで、成形品の表面硬度を高めるために、従来、高硬
度のガラス粉末を充填材として樹脂組成物に配合する方
法が広く採用されている。この方法によれば、成形品の
表面硬度を高めることができるが、前述したＳＭＣやＢ
ＭＣにて成形するときは、近年、人造大理石に求められ
るに至っている透明感や表面平滑性等に代表される高級
感を有する製品を得ることは困難である。Therefore, in order to increase the surface hardness of a molded article, a method of blending a high hardness glass powder as a filler into a resin composition has been widely adopted. According to this method, the surface hardness of the molded product can be increased, but the above-mentioned SMC and B
When molding with MC, it is difficult to obtain a product that has a high-class feel typified by transparency and surface smoothness, which have recently been sought after for artificial marble.
他方、得られる成形品に表面平滑性を与えるためには、
従来、金型を高温にしてプレス成形したり、或いは粒径
の小さい充填材を用いる等の方法が採用されている。、
しかし、この方法によれば、得られる成形品は透明感を
もたない。On the other hand, in order to give the resulting molded product surface smoothness,
Conventionally, methods such as pressing a mold at a high temperature or using a filler with a small particle size have been adopted. ,
However, according to this method, the molded product obtained does not have transparency.
このように、従来の方法によれば、透明感と表面平滑性
を共に有すると共に、表面硬度にもすぐれる人造大理石
を得ることは困難である。Thus, according to conventional methods, it is difficult to obtain artificial marble that has both transparency and surface smoothness, and also has excellent surface hardness.
（発明が解決しようとする課Ｈ）
本発明は、従来の人造大理石の製造における上記した問
題を解決するためになされたものであって、充填材とし
てガラス粉末を用いて、そのすぐれた表面硬度を保持し
つつ、透明性及び表面平滑性にすぐれる人造大理石を得
ることができる人造大理石用不飽和ポリエステル樹脂組
成物を提供することを目的とする。(Problem H to be solved by the invention) The present invention has been made to solve the above-mentioned problems in the production of conventional artificial marble, and uses glass powder as a filler to achieve excellent surface hardness. An object of the present invention is to provide an unsaturated polyester resin composition for artificial marble, which can obtain artificial marble with excellent transparency and surface smoothness while maintaining the following properties.
（課題を解決するための手段）
本発明による人造大理石用樹脂組成物は、不飽和ポリエ
ステル樹脂１００重量部に対して、平均粒径１０μｍ以
下のガラス粉末と平均粒径３０〜４０μｍのガラス粉末
と平均粒径６０〜８０μｍのガラス粉末とを合計量にて
１５０〜４００重量部を含有し、且つ、上記ガラス粉末
の配合割合は、平均粒径゛３０〜４０μｍのガラス粉末
７５〜９２重量％と平均粒径６０〜８０μｍのガラス粉
末２５〜８重量％とからなるガラス粉末５〜３０重量％
に対して、平均粒径１０μｍ以下のガラス粉末９５〜７
０重量％であることを特徴とする。(Means for Solving the Problems) The resin composition for artificial marble according to the present invention contains glass powder with an average particle size of 10 μm or less and glass powder with an average particle size of 30 to 40 μm to 100 parts by weight of an unsaturated polyester resin. It contains a total of 150 to 400 parts by weight of glass powder with an average particle size of 60 to 80 μm, and the blending ratio of the glass powder is 75 to 92 weight % of glass powder with an average particle size of 30 to 40 μm. 5-30% by weight of glass powder consisting of 25-8% by weight of glass powder with an average particle size of 60-80 μm
Glass powder with an average particle size of 10 μm or less 95-7
It is characterized by being 0% by weight.
不飽和ポリエステル樹脂は、通常、不飽和ポリエステル
５０〜８０重量％と重合性単量体５０〜２０重量％とか
らなる。不飽和ポリエステルが５０重量％よりも少ない
ときは、十分な強度をもつ人造大理石を得ることができ
ず、他方、８０重量％を越えるときは、樹脂組成物の成
形性及び作業性が悪化する。The unsaturated polyester resin usually consists of 50 to 80% by weight of unsaturated polyester and 50 to 20% by weight of polymerizable monomer. When the unsaturated polyester content is less than 50% by weight, artificial marble with sufficient strength cannot be obtained, while when it exceeds 80% by weight, the moldability and workability of the resin composition deteriorate.
不飽和ポリエステル樹脂は、一般に、α、β−不飽和二
塩基酸及び／又はその酸無水物である酸成分と多価アル
コール成分とを反応させることによって得ることができ
る。An unsaturated polyester resin can generally be obtained by reacting an acid component, which is an α,β-unsaturated dibasic acid and/or its acid anhydride, with a polyhydric alcohol component.
α、β−不飽和二塩基酸としては、例えば、マレイン酸
、フマル酸、イタコン酸、シトラコン酸、クロルマレイ
ン酸等を挙げることができ、これらは２種以上を併用し
てもよい、多価アルコールとしては、例えば、エチレン
グリコール、ジエチレングリコール、プロピレングリコ
ール、ジプロピレングリコール、１．３−ブタンジオー
ル、ネオペンチルグリコール、１，６−ヘキサンジオー
ル、トリエチレングリコール、水素添加ビスフェノール
Ａ、イソペンチルグリコール、グリセリン、トリメチロ
ールプロパン、ジシクロペンタジェン等を挙げることが
できる。これらも２種以上を併用してもよい。Examples of α,β-unsaturated dibasic acids include maleic acid, fumaric acid, itaconic acid, citraconic acid, and chlormaleic acid. Examples of the alcohol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, neopentyl glycol, 1,6-hexanediol, triethylene glycol, hydrogenated bisphenol A, isopentyl glycol, and glycerin. , trimethylolpropane, dicyclopentadiene, and the like. These may also be used in combination of two or more.
不飽和ポリエステル樹脂の製造において、酸成分として
、必要に応じて、飽和二塩基酸及び／又はその酸無水物
を併用してもよい。このような飽和二塩基酸としては、
例えば、フタル酸、イソフタル酸、テレフタル酸、トリ
メリット酸、コハク酸、アゼライン酸、アジピン酸、テ
トラヒドロフタル酸、ヘキサヒドロフタル酸、クロレン
デイツク酸、テトラクロロフタル酸、テトラブロモフタ
ル酸等を挙げることができる。In the production of unsaturated polyester resins, a saturated dibasic acid and/or its acid anhydride may be used in combination as the acid component, if necessary. Such saturated dibasic acids include
Examples include phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, succinic acid, azelaic acid, adipic acid, tetrahydrophthalic acid, hexahydrophthalic acid, chlorendic acid, tetrachlorophthalic acid, tetrabromophthalic acid, etc. can.
他方、重合性単量体としては、スチレン、ビニルトルエ
ン、ジビニルベンゼン、α−メチルスチレン、クロルス
チレン、ジクロルスチレン、酢酸ビニル、ジアリルフタ
レート、ジアリルイソフタレート、ジアリルテレフタレ
ート等、不飽和ポリエステル樹脂と架橋可能なビニル単
量体、ジビニル単量体、ビニルオリゴマー等を挙げるこ
とができる０通常、スチレンが好ましく用いられる。On the other hand, examples of polymerizable monomers include styrene, vinyltoluene, divinylbenzene, α-methylstyrene, chlorostyrene, dichlorostyrene, vinyl acetate, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, etc., which are crosslinked with unsaturated polyester resins. Possible vinyl monomers, divinyl monomers, vinyl oligomers, etc. may be mentioned. Usually, styrene is preferably used.
本発明による人造大理石用樹脂組成物においては、無機
質充填材として、不飽和ポリエステル樹脂１００重量部
に対して、平均粒径１０μｍ以下、好ましくは３μｍ以
上のガラス粉末と平均粒径３０〜４０μｍのガラス粉末
と平均粒径６０〜８０μｍのガラス粉末とが合計量にて
１５０〜４００重量部の範囲で用いられる。ガラス粉末
の合計量が１５０重量部未満の場合は、樹脂組成物の粘
度が低すぎて成形性が悪くなり、４００重量部を越える
と、ガラス粉末の分散性が不十分となって、樹脂組成物
が塊状となり、成形性が悪くなる。In the resin composition for artificial marble according to the present invention, glass powder with an average particle size of 10 μm or less, preferably 3 μm or more and glass with an average particle size of 30 to 40 μm are used as the inorganic filler, based on 100 parts by weight of the unsaturated polyester resin. The powder and the glass powder having an average particle size of 60 to 80 μm are used in a total amount of 150 to 400 parts by weight. If the total amount of glass powder is less than 150 parts by weight, the viscosity of the resin composition will be too low, resulting in poor moldability; if it exceeds 400 parts by weight, the dispersibility of the glass powder will be insufficient, resulting in poor resin composition. The product becomes lumpy and has poor moldability.
ここに、本発明によれば、上記ガラス粉末の配合割合は
、平均粒径３０〜４０μｍのガラス粉末７５〜９２重量
％と平均粒径６０〜８０μｍのガラス粉末２５〜８重量
％とからなるガラス粉末５〜３０重量％に対して、平均
粒径１０μｍ以下のガラス粉末９５〜７０重量％であり
、このように平均粒径の異なるガラス粉末を上記所定の
割合で樹脂組成物に用いることによって、すぐれた表面
硬度を確保しつつ、透明性及び表面平滑性にすぐれる人
造大理石を得ることができる。According to the present invention, the blending ratio of the glass powder is 75 to 92% by weight of glass powder with an average particle size of 30 to 40 μm and 25 to 8% by weight of glass powder with an average particle size of 60 to 80 μm. By using glass powder with an average particle size of 10 μm or less in the resin composition in the predetermined ratio, 95 to 70% by weight of glass powder with an average particle size of 10 μm or less is based on 5 to 30% by weight of the powder. Artificial marble with excellent transparency and surface smoothness can be obtained while ensuring excellent surface hardness.
平均粒径３０〜４０μｍのガラス粉末と平均粒径６０〜
８０μｍのガラス粉末との合計量がガラス粉末全体の３
０重量％を越えるときは、得られる成形品の表面平滑性
が悪くなり、他方、平均粒径１０μｍ以下のガラス粉末
がガラス粉末全体の９５重量％を越えるときは、得られ
る成形品が透明性に乏しくなる。Glass powder with an average particle size of 30~40μm and an average particle size of 60~
The total amount of 80μm glass powder is 3% of the total glass powder.
If it exceeds 0% by weight, the surface smoothness of the molded product obtained will deteriorate, and on the other hand, if the glass powder with an average particle size of 10 μm or less exceeds 95% by weight of the total glass powder, the molded product obtained will have poor transparency. becomes scarce.
本発明による人造大理石用不飽和ポリエステル樹脂は、
通常、硬化剤を含有し、更に、必要に応じて、補強材、
低収縮材、硬化促進剤、内部離型剤、増粘剤、着色剤等
を含有する。The unsaturated polyester resin for artificial marble according to the present invention is
Usually contains a hardening agent, and if necessary, a reinforcing material,
Contains low shrinkage material, curing accelerator, internal mold release agent, thickener, coloring agent, etc.
硬化剤として、例えば、ｔ−ブチルパーベンゾエート、
ベンゾイルパーオキサイド、メチルエチルケトンパーオ
キサイド、ジクミルパーオキサイド、ｔ−ブチルパーオ
キシ−２−エチルヘキサノエート、１．１−ジ−ｔ−ブ
チルパーオキシシクロヘキサン、ｔ−ブチルパーオキシ
イソプロピルカーボネート等の有機過酸化物が用いられ
る。As a curing agent, for example, t-butyl perbenzoate,
Organic filters such as benzoyl peroxide, methyl ethyl ketone peroxide, dicumyl peroxide, t-butylperoxy-2-ethylhexanoate, 1,1-di-t-butylperoxycyclohexane, t-butylperoxyisopropyl carbonate, etc. Oxides are used.
補強材としては、ガラス繊維、ポリエステル繊維、フェ
ノール繊維、ポリビニルアルコール繊維、炭素繊維等を
挙げることができるが、通常、ガラス繊維が好ましく用
いられる。Examples of the reinforcing material include glass fibers, polyester fibers, phenol fibers, polyvinyl alcohol fibers, and carbon fibers, but glass fibers are usually preferably used.
また、低収縮材としては、例えば、ポリエチレン、ポリ
スチレン、ポリメタクリル酸メチル、ポリ塩化ビニル、
ポリ酢酸ビニル、ポリカプロラクタム、飽和ポリエステ
ル等の熱可塑性樹脂、ポリブタジェンゴム、ポリスチレ
ン−アクリロニトリル共重合体等が用いられる。In addition, examples of low shrinkage materials include polyethylene, polystyrene, polymethyl methacrylate, polyvinyl chloride,
Thermoplastic resins such as polyvinyl acetate, polycaprolactam, and saturated polyester, polybutadiene rubber, and polystyrene-acrylonitrile copolymers are used.
硬化促進剤としては、有機酸の金属塩、特に、コバルト
塩、例えば、ナフテン酸コバルト、オクチル酸コバルト
、アセチルアセトンコバルト等が用いられる。As the curing accelerator, metal salts of organic acids, particularly cobalt salts, such as cobalt naphthenate, cobalt octylate, cobalt acetylacetone, etc., are used.
内部離型剤としては、ステアリン酸、ステアリン酸亜鉛
等の高級脂肪酸や高級脂肪酸塩、アルキルリン酸エステ
ル等が用いられる。As the internal mold release agent, higher fatty acids such as stearic acid and zinc stearate, higher fatty acid salts, alkyl phosphates, and the like are used.
増粘剤は、不飽和ポリエステルが有する水酸基、カルボ
キシル基やエステル基等と化学的に結合し、線状又は一
部交叉結合を生ぜしめて、分子量を増大させ、不飽和ポ
リエステル樹脂を増粘させるものであって、例えば、ト
ルエンジイソシアネートのようなジイソシアネート類、
アルミニウムイソプロポキシド、チタンテトラブトキシ
ドのような金属アルコキシド、酸化マグネシウム、酸化
カルシウム、酸化ブリリウムのような二価金属の酸化物
、水酸化カルシウムのような二価金属の水酸化物等が用
いられる。Thickeners are substances that chemically bond with hydroxyl groups, carboxyl groups, ester groups, etc. possessed by unsaturated polyester, creating linear or partially cross-linked bonds to increase the molecular weight and thicken the unsaturated polyester resin. For example, diisocyanates such as toluene diisocyanate,
Metal alkoxides such as aluminum isopropoxide and titanium tetrabutoxide, divalent metal oxides such as magnesium oxide, calcium oxide, and bryllium oxide, and divalent metal hydroxides such as calcium hydroxide are used.
本発明による人造大理石用樹脂組成物は、通常、上述し
たような不飽和ポリエステル樹脂と充填材とを混練し、
更にこれに上述したような硬化剤、その他必要に応じて
、補強材、低収縮材、硬化促進剤、内部離型剤、増粘剤
、着色剤等を混合することによって得ることができる。The resin composition for artificial marble according to the present invention is usually obtained by kneading the above-mentioned unsaturated polyester resin and a filler,
Furthermore, it can be obtained by mixing the above-mentioned curing agent and other materials such as a reinforcing material, a low shrinkage material, a curing accelerator, an internal mold release agent, a thickener, a coloring agent, etc. as necessary.
本発明による人造大理石用樹脂組成物は、通常、成形温
度１２０〜１６０°Ｃ１成形圧カフ０〜１４０ ｋｇ／
ａｉでプレス成形することによって、人造大理石を得る
ことができる。The resin composition for artificial marble according to the present invention usually has a molding temperature of 120 to 160°C and a molding pressure of 0 to 140 kg/c.
Artificial marble can be obtained by press molding using AI.
（実施例） 以下に実施例を挙げて本発明を説明する。(Example) The present invention will be explained below with reference to Examples.
実施例１〜４
充填材として平均粒径５μｍと３５μｍと７５μｍのガ
ラス粉末をそれぞれ所定割合で用いて、第１表に示す組
成を有するＢＭＣを調製し、成形温度１３０℃、成形圧
力１００ ｋｇｆ／ｃｍｚ、成形時間７分の条件で成形
し、厚さ６１１ＩＩｌの平板を得た。Examples 1 to 4 BMC having the composition shown in Table 1 was prepared using glass powders with average particle diameters of 5 μm, 35 μm, and 75 μm at predetermined ratios as fillers, and the molding temperature was 130° C. and the molding pressure was 100 kgf/ cmz and a molding time of 7 minutes to obtain a flat plate with a thickness of 611 IIl.
この成形品についての特性を第１表に示す。The properties of this molded article are shown in Table 1.
比較例１〜３
充填材として平均粒径５μｍと３５μｍと７５μｍのガ
ラス粉末のいずれか一種を用い、又はこれらを本発明に
よる条件を満たさない割合で用いて、第１表に示す組成
を有するＢＭＣを調製し、実施例１と同じ条件で成形し
、厚さ６ｍｍの平板を得た。この成形品についての特性
を第１表に示す。Comparative Examples 1 to 3 BMC having the composition shown in Table 1 using any one of glass powders with average particle diameters of 5 μm, 35 μm, and 75 μm as a filler, or using these in a proportion that does not satisfy the conditions according to the present invention. was prepared and molded under the same conditions as in Example 1 to obtain a flat plate with a thickness of 6 mm. The properties of this molded article are shown in Table 1.
第１表に示す結果から明らかなように、本発明の樹脂組
成物によれば、透明性及び表面平滑性にすぐれるのみな
らず、表面硬度にもすぐれる成形品を得ることができる
。As is clear from the results shown in Table 1, according to the resin composition of the present invention, molded articles not only excellent in transparency and surface smoothness but also excellent in surface hardness can be obtained.
（発明の効果）
本発明による人造大理石用樹脂組成物は、以上のように
、不飽和ポリエステル樹脂と共に、平均粒径の異なるガ
ラス粉末を所定の割合で含むので、すぐれた表面硬度を
確保しつつ、透明性と表面平滑性にすぐれる人造大理石
を得ることができる。(Effects of the Invention) As described above, the resin composition for artificial marble according to the present invention contains glass powder with different average particle sizes in a predetermined ratio together with an unsaturated polyester resin, so that it can maintain excellent surface hardness while ensuring excellent surface hardness. , it is possible to obtain artificial marble with excellent transparency and surface smoothness.
従って、このような樹脂組成物は、例えば、浴槽、洗面
カウンター、キッチンカウンター、テーブル等の製造に
好適である。Therefore, such a resin composition is suitable for manufacturing, for example, bathtubs, washroom counters, kitchen counters, tables, and the like.
特許出願人 積水化学工業株式会社 代表者 廣１） 馨Patent applicant Sekisui Chemical Co., Ltd. Representative Hiro 1) Kaoru
Claims (1)
平均粒径１０μｍ以下のガラス粉末と平均粒径３０〜４
０μｍのガラス粉末と平均粒径６０〜８０μｍのガラス
粉末とを合計量にて１５０〜４００重量部を含有し、且
つ、上記ガラス粉末の配合割合は、平均粒径３０〜４０
μｍのガラス粉末７５〜９２重量％と平均粒径６０〜８
０μｍのガラス粉末２５〜８重量％とからなるガラス粉
末５〜３０重量％に対して、平均粒径１０μｍ以下のガ
ラス粉末９５〜７０重量％であることを特徴とする人造
大理石用樹脂組成物。(1) For 100 parts by weight of unsaturated polyester resin,
Glass powder with an average particle size of 10 μm or less and an average particle size of 30 to 4
Contains a total of 150 to 400 parts by weight of glass powder of 0 μm and glass powder of average particle size of 60 to 80 μm, and the blending ratio of the glass powder is such that the average particle size of glass powder is 30 to 40 μm.
μm glass powder 75-92% by weight and average particle size 60-8
1. A resin composition for artificial marble, characterized in that the content is 95 to 70% by weight of glass powder with an average particle size of 10 μm or less relative to 5 to 30% by weight of glass powder consisting of 25 to 8% by weight of glass powder of 0 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2294916A JPH0717426B2 (en) | 1990-10-30 | 1990-10-30 | Resin composition for artificial marble |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2294916A JPH0717426B2 (en) | 1990-10-30 | 1990-10-30 | Resin composition for artificial marble |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04170351A true JPH04170351A (en) | 1992-06-18 |
| JPH0717426B2 JPH0717426B2 (en) | 1995-03-01 |
Family
ID=17813913
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2294916A Expired - Lifetime JPH0717426B2 (en) | 1990-10-30 | 1990-10-30 | Resin composition for artificial marble |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0717426B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100396834B1 (en) * | 1996-12-19 | 2004-02-14 | 주식회사 효성 | Thermosetting unsaturated polyester resin composition |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6469311A (en) * | 1987-09-11 | 1989-03-15 | Ferro Enamels Japan | Unsaturated polyester resin press-molded article with improved transparency and manufacture thereof |
| JPH02153966A (en) * | 1988-12-07 | 1990-06-13 | Nippon Fueroo Kk | Glittering resin molding material and molded article |
| JPH02233571A (en) * | 1989-03-03 | 1990-09-17 | Toto Ltd | Stone-textured artificial stone |
-
1990
- 1990-10-30 JP JP2294916A patent/JPH0717426B2/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6469311A (en) * | 1987-09-11 | 1989-03-15 | Ferro Enamels Japan | Unsaturated polyester resin press-molded article with improved transparency and manufacture thereof |
| JPH02153966A (en) * | 1988-12-07 | 1990-06-13 | Nippon Fueroo Kk | Glittering resin molding material and molded article |
| JPH02233571A (en) * | 1989-03-03 | 1990-09-17 | Toto Ltd | Stone-textured artificial stone |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100396834B1 (en) * | 1996-12-19 | 2004-02-14 | 주식회사 효성 | Thermosetting unsaturated polyester resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0717426B2 (en) | 1995-03-01 |
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